Disazo and metallized disazo dyes containing a monochlorotriazine substituent



United States Patent 3,259,618 DISAZO AND METALLIZED DISAZO DYES CONTAINING A MONOCHLOROTRIAZINE SUBSTITUENT Herbert Francis Andrew, Manchester, England, assignor to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Original application Nov. 16, 1959, Ser. No. 852,982. Divided and this application July 3, 1963, Ser. No. 292,754 Claims priority, application Great Britain, Nov. 28, 1958, 38,435/58 4 Claims. (Cl. 260-146) This application is a continuation-in-part of application Serial No. 183,712 filed March 30, 1962 and noW abandoned, which itself is a divisional of application Serial No. 852,982, filed November 16, 1959, now Patent No. 3,038,893.

The subject matter of the present application is concerned with selected dyestufis of the broad class of azo dyestuffs which, in the form of the free acids are represented by the formula:

5 4 P soar), I)

wherein A represents an aryl radical which does not contain a hydroxy group in an ortho position to the azo link, P represents a group of the formula:

which is attached to the 6- or 7-position of the naphthalene nucleus, R represents a substituted or unsubstituted phenylene radical, R represents a hydrogen atom or an alkyl radical, X represents a chlorine or a bromine atom, Y represents a chlorine or a bromine atom or an alkoxy, alkyl, aryl, aryloxy, arylmercapto or alkylmercapto radical, or a thiocyano, amino or substituted amino group, m and p each represent 1 or 2 and may be the same or different provided that m is not 2 when p is 1, n represents a whole number and the phenylene or naphthylene radical represented by B may contain substituents.

In further defining this broad class by way of example, as examples of the aryl radicals represented by A there may be mentioned monocyclic aryl radicals such as phenyl, sulphophenyl, carboxyphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, methylphenyl, nitrophenyl, benzeneazophenyl, sulphophenylazophenyl, acetylaminophenyl, benzoylaminophenyl and sulphocarboxyphenyl radicals and bicyclic aryl radicals such as naphthyl, sulphonaphthyl, disulphonaphthyl, methoxynaphthy-l and ethoxynaphthyl radicals.

Further, as examples of the substituents which may be present in the phenylene or naphthylene radical B in said broad class there may be mentioned alkoxy for example lower alkoxy such as methoxy and ethoxy, alkyl for example lower alkyl such as methyl, carboxy, acylamino such acetylamino and benzoylamino, and sulpho.

Further, as examples of the substituted phenylene radicals represented by R in said broad class there may be mentioned 2-sulpho-1z4-phenylene and 2-sulpho-1z3- phenylene, and as examples of the alkyl radicals represented by R in said broad class there may be mentioned 3,259,618 Patented July 5, 1966 "ice lower alkyl radicals such as methyl, ethyl, propyl and butyl.

As examples of the radicals and groups represented by Y in said broad class there may be mentioned alkyl radicals for example lower alkyl radicals such as methyl and ethyl, aryl radicals for example monocyclic aryl radicals such as phenyl and tolyl, alkoxy radicals for example lower alkoxy radicals such as methoxy, propoxy and ethoxy, aryloxy radicals for example monocyclic aryloxy radicals such as ph'enoxy and sulphophenoxy, alkylmercapto radicals for example lower alkylmercapto radicals such as m'ethylmercapto, arylmercapto radicals for example monocy-clic earylmercapto radicals such as phenylmercapto, and substituted amino groups such as methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, N-methyl-N-ethylamino, N-ethyl-N-propylamino, B-hydroxyethylamino, -di(fi-hydroxyethyl)amino, phenylamino, 2-sulphophenylamino, 3-sulphophenylamino, 4-sulphophenylamino, disulphophenylamino, 3-carboxyphenylamino, 4-carboxyphenylamino, naphthylarnino, sulphonaphthylamino, disulphonaphthylamino, benzylamino, piperidyl, N-methyl-N-B- hydroxyethylamino, N ethyl N B hydroxyethylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-p-hydroxyethyl-N-phenylamino, 2:5 -di carboxyphenylamino, N-methyl-N-3'-sulphophenylamino, N-ethyl N 4 sulphophenylamino, N ,8 hydroxy N 3- sulphophenylamino, 3- or 4-methoxyphenylamino, 2-, 3-, or 4-methylphenylamino, 4-chlorophenylamino, 4methyl 3 sulphophenylamino, 4 chloro 3 sulphophenylamino and 3-carboxy-S-sulphophenylamino, but it is preferred that Y represents a chlorine atom or a sulphophenylamino or a disulphophenylamino group such as a 3 :5-disu1phophenylamino group.

The whole number represented by n in said broad class is preferably a whole number not greater than 6 so that when n represents a whole number from 2 to 6 the C H group represents a lower alkyl radical, or preferably n represents 1 so that the C H group represents a hydrogen atom. It is also preferred that m and p each represent 1.

As stated. above, the present application is concerned with a class of disazo dyestuffs selected from the broad class of dyestuffs so defined. The dyestuffs of the presently claimed invention are in part the disazo compounds represented by the following formula:

wherein A, Q, X, R and Y have the meanings stated below, and the -NR group is attached to the 6- 0r 7-position of the naphthalene nucleus, and for the remainder are the 1:1 complex copper compounds of said disazo compounds.

In the above formula, A represents a dior trisulphonaphthyl radical or a phenyl radical which contains a carboxy group or one or two sulphonic acid groups or contains both a sulphonic acid group and in addition from 1 to 2 further substituents selected from carboxy, methyl, methoxy and chlorine; Q represents a hydrogen atom, a methyl group or a methoxy group; X represents a methoxy or a carboxy group; R represents a hydrogen atom or a methyl group; and Y is one of the radicals: amino, lower alkylamino, fi-hydroxyethylamino, methoxy, phenoxy, anilino, monoand di-sulphoanilino, diand tri-sulfonaphwherein A, X and Q have the meanings stated above, and coupling the diazo compound so obtained with a coupling component of the formula:

wherein R and Y have the meanings stated above.

This process can be conveniently carried out by adding sodium nitrite to a solution or suspension of the amine of Formula IV in a dilute aqueous solution of hydrochloric acid, adding the diazo solution or suspension so obtained to, an aqueous solution of the coupling component of Formula V, adding sodium carbonate to maintain the pH of the mixture between 6.5 and 7 and filtering off the azo dyestutf which is precipitated. If desired sodium chloride can be added to ensure complete precipitation of all the azo dyestulf.

The amines of Formula 1V can themselves be obtained by diazotising a primary amine of the formula: A-NH wherein A has the meaning stated above and coupling the diazo compound so obtained with a para coupling amine of the formula:

wherein Q and X have the meaning stated above.

As examples of the primary amines of the formula: ANH which may be used there may be mentioned orthanilic acid, metanilic acid, sulphanilic acid, 2:5-dichloroaniline-4-sulphonic acid, -chloro-4-methylaniline- 2-sulphonic acid, 4-methoxyaniline-Z-sulphonic acid, 3- chloro-4-methylaniline-Z-sulphonic acid, 4-chloroaniline- 2-sulphonic acid, 4-chloro-3-methylaniline-6-sulphonic acid, 4-chloroaniline-3-sulphonic acid, aniline 2:4 disulphonic acid, aniline-2:5-disulphonic acid, anthranilic acid, 5-sulpho-anthranilic acid, 4-sulphoanthranilic acid, Z-naphthylamine 1:5-, 316-, 4:8-, 5:7- or 6:8-disulphonic acid, and 4-sulpho-2-aminoanisole.

As examples of the para coupling amines which may be used there may be mentioned 2-methoxy-S-methylaniline, 2:5-dimethoxyaniline, anthranilic acid and o-anisidine.

The coupling components of Formula V may themselves be obtained by treating a compound of the formula:

S OITI (VII) wherein R has the meaning stated above, and the NI-IR group is attached to the 6- or 7-position of the naphthalene nucleus, with a triazine of the formula:

r r YC CCl wherein Y has the meaning stated above.

As examples of the compounds of Formula VII which can be used there may be mentioned 2-amino-5-naphthol- 1:7-disulphonic acid, 2-amino-8-naphthol-3:6-disulphonic acid and Z-methylamino-S-naphthol-1:7-disulphonic acid.

As examples of the triazines of Formula VIII which can be used there may be mentioned (VIII) 2-methoxy-4z6-dichloro-1 :3 :5 -triazine,

2-amino-4: 6-dichloro-l :3 :5 -triazine,

2-methylamino-4:6-dichloro-1 :3 :5 -triazine,

2-diethylamino-4: 6-dichloro-1 :3 :5 -triazine,

2-phenylamino-4:6-dichloro-1z3z5-triazine,

2-(2'-sulphophenylamino) -4:6-dichlor0-l z3z5-triazine,

2-( 3'-sulphophenylamino)-4:6-dichloro-l :3 :5 -triazine,

2- (4'-sulphophenylamino)-4:6-dichloro-lz3z5-triazine,

and

2-phenoxy-4:6-dichloro-1:3:5-triazine.

The azo dyestuifs of Formula III can also be obtained by condensing an azo compound of the formula:

I N HR wherein A, X, Q and R have the meanings stated above, with a triazine of Formula VIII as hereinbefore defined; by using instead the 1:1 copper complex of an azo compound of Formula IX, there is obtained a 1:1 copper complex of the dyestufl' of Formula HI.

This alternative process can be conveniently carried out by adding an aqueous solution of the azo compound of Formula IX or its copper complex to a suspension of the triazine of Formula VIII in a mixture of acetone and water, adding sodium carbonate to maintain the pH of the mixture between 5 and 7.5, and filtering oi? the azo dyestufi which is precipitated. If desired, sodium chloride can be added to ensure complete precipitation of all the azo dyestufi.

The azo compounds of Formula IX used in this alternative process can be obtained by coupling a diazotised amine of Formula IV with a compound of Formula VII, and the copper complexes of these compounds can be obtained by treatment of the compound with a hot, aqueous solution of cupramrnonium sulphate.

The azo dyestulfs of Formula III or the 1:1 copper complex of such a dyestutf, can also be obtained by treating a dyestuff of Formula III or its copper complex wherein Y represents a chlorine atom and A, Q, X and R have the meanings stated above with one of the compounds: ammonia; a lower alkylamine; B-hydroxyalkylamine; aniline; an aniline monoor di-sulphonic acid; a naphthylamine monoor di-sulphonic acid; and aniline monoor di-sulphonic acids containing one to two radicals selected from hydroxyl and carboxylic acid.

This process can be conveniently carried out by heating an aqueous solution of the dyestuff or its copper complex wherein Y represents a chlorine atom with one molecular proportion of the said compound at a temperature between 40" and 45 0., adding sodium carbonate to maintain the pH of the mixture between 7.0 and 7.2, adding sodium chloride and filtering off the dyestuff which is precipitated.

The azo dyestulf of Formula III and their 1:1 copper complexes are purple and reddish-blue dyes. They are valuable for colouring cellulose textile materials, for example cotton, viscose rayon and linen textile materials. For colouring these materials the new dyestuffs may be applied by dyeing or printing methods, preferably in con- '6 agent, the dyestuff yields violet shades with good fastness to light and to washing.

The following table gives further examples of the shades obtained on cellulose textile materials from other dyejunction with a treatment with an acid-binding agent, for 5 stufis of the invention which are obtained by replacing example by the methods disclosed in United States Patent No. 2,892,671. When so applied the new dyestulis and their copper complexes are capable of building up to give strong violet to navy-blue shades possessing very good the 11.7 parts of the trisodium salt of the aminodisazo compound used in the above example by an equivalent amount of the sodium salt of the aminoazo compound which is obtained by diazotising the primary amine listed fastness to light and to wet treatments such as washing, 19 in the second column of the table, coupling with the paraand hy-pochlorite bleach. The coloured fabrics have excellent storage stability and are highly resist-ant to the dye-to-fa'bric hydrolytic effect sometimes found in cellulose fabrics coloured With reactive dyes.

coupling amine listed in the third column, diazotising and coupling With the coupling component listed in the fourth column of the table, and by replacing the 3.8 parts of the sodium salt of 3-sulphoaniline by an equivalent amount The invention is illustrated but not limited by the folof the amine listed in the fifth column of the table.

Shade on Example Primary Amine Para-coupling Amine Coupling Component Amine c Ie llultlise exti e Materials Z-Sulphoaniline Z-methoxyaniline 2-amino-5-naphthol-1z7- 2-naphthylamine-4;8-disul- Violet.

disulphonic acid. phonic acid. 2:5-disulphoani1ine 2-methoxy-5-methy1aniline do Aniline Do. 2-naphthylamine-4:S-disul- 2:5-dimethoxyaniline do 3: 5-disu1phoaniline Do.

phonic acid. 2-napl1thylamine3z6z8- 2'methoxy-emethylaniline. -.do 3-sulphoaniline Do.

trisulphonic acid. 2-naphthylamine4z8-disul- Z-carboxyaniline 2-amino-8-naphthol-3z6- 5-sulpho-2-amino benzoic Do. phonic acid. disulphonic acid. acid. 2:5-disu1phoaniline 2-methoxy-5-methylaniline do Ammonium hydroxide Do. Kohlqrodmethyl-G-sulpho- 2-methoxyani1ine do 5-sulpho-2-amino benzoic Do.

ani ine. acid. 2:5-disu1phoaniline 2-methoxy-5-methylaniline- 2-amino-5-naphthol-1z7- 3-sulphoaniline Do.

disulphonic acid. 4 methoxyaniline-?rsuldo do et-sulphoaniline D0.

phonic acid. 3-chloro+methyl-6-sulpho do do 5su1pho-2-aminobenzoic Do.

aniline. aci Zsulphoaniline do 2-amino-8-naphthol-3z6- 3:5-disulphoani1ine Do.

disulphonic acid. 2-.5-dichloro4-sulphoanilinedo -sulgho-Z-aminobenzoic Do.

aci 5-su1pho-2-aminobenzoic Z-amino-5-naphthol-1 :7- 3-arnino-5-sulpho-2-hydr0xy- D 0.

acid. disulphonic acid. benzoic acid. 15 2:5-disulphoaniline Ammonium hydroxide Do. 16 do Methylamine Do. 17. d0 -..do B-Hydroxyethylamine Do. 18 4-methyl-2-su1phoaniline 2-ainino-8-naphthol-3:6- 4-sulpho-2-aminobenzoic Do.

disulphonic acid. acid. 19 2-arninohenzoic acid s do -1 3:5-disulphoaniline Do. 20 2-su1phoaniline 2-Nmethylamino-5-naph- 4-sulphoaniline Do.

thol-l :7-disulphonic acid. 21 4-chloroaniline-2-sulphonic 2 amino-8-naphthol-3z6- 3-sulphoaniline Do.

aci disulphonic acid. 22 2-sulphoanilinc 2-methylamino-S-naphthol- Ammonia Do.

3zfi disulphonic acid.

lowing examples in which the parts and percentages are Example 23 by weight:

Example 1 Diazotised orthanilic acid is coupled with 2-methoxy- S-methylaniline and the aminoazo compound so obtained is diazotised and coupled under alkaline conditions with an equimolecular proportion of 2-amino-8-naphthol-3z6- disulphonic acid.

A solution of 11.7 parts of the trisodium salt of the amino-disazo compound so obtained in 400 parts of water is added with stirring to a suspension of 3.25 parts of cyanuric chloride in a mixture of 50 parts of acetone, 180 parts of ice and 100 parts of water, the temperature being maintained between 0 and 5 C. by external cooling. The mixture is stirred for 1% hours then neutralised to pH 6.8 with 12 parts of a 10% aqueous solution of sodium carbonate. A solution of 3.8 parts of the sodium salt of 3-sulphoaniline in parts of Water is added to the solution of dichlorotriazinylamino compound and the mixture is then heated for 3 hours at a temperature between and C. The pH of the solution being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. 60 parts of sodium chloride are then added and the dyestufi which is precipitated is filtered oil and dried.

On analysis the dyestuff so obtained is found to contain 0.95 atom of organically bound chlorine for each disazo molecule present. When applied to cellulose textile materials in conjunction with a treatment with an acid-binding Diazotised orthanilic acid is coupled with Z-methoxy- S-methylaniline and the aminoazo compound so obtained is diazotised and coupled under alkaline conditions with an equimolecular proportion of 2-amino-8-naphthanol- 3:6-disulphonic acid. 7

A solution of 17.4 parts of the trisodium salt of the aminodisazo compound so obtained in 400 parts of water is added with stirring to a suspension of 4.6 parts of 2-methoxy-4:6-dichlorotriazine in a mixture of 40 parts of acetone and 100 parts of water and the mixture is then stirred at a temperature between 35 and 45 C. for 2 hours the pH of the mixture being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. parts of sodium chloride are then added and the dyestuff which is precipitated is filtered off, washed with 15 parts of Water and dried. 0n analysis, the dyestuff so obtained is found to contain 0.85 atom of organically bound chlorine for each disazo molecule present. When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestufi? yields violet shades having good fastness to Washing and to light.

Example 24 By'replacing the 4.6 parts of 2-methoxy-4z6-dichlor0- triazine used in Example 23 by 6.1 parts of 2-phenoxy- 4:6-dichlortitriazine there is obtained a dyestulf which contains 0.98 atom of organically bound chlorine for each [binding agent yields navy-blue shades possessing good fastness to washing and to light.

Example 28 Diazotised orthanilic acid is coupled with Z-methoxy-S- The mixture is To the solution of dichlorotriazinylamino 90 parts of sodium chloride sulphoanilino)-4:6-dichlorotriazine used in Example 25 there are used 6.4 parts of 2-phenoxy-4:6-dichlorotriazine. The dyestufi? so obtained, when applied to cellulose textile materials in conjunction with a treatment with an acid- When applied to cellulose textile ma- Example 25 methylaniline, the aminoazo compound so obtained is ditisted and coupled under alkaline conditions with an Diazotised anrlme-ZzS-drsulphomc acid is coupled with Z-methoxy-S-methylaniline, the :aminoazo compound so 2 1 3 2 9 P FE g i gy i obtained is diazotised and coupled under alkaline condit o p e ammo lsazo compmin tions with an equimolecular proportion of 2-amino-5- 10 obtamed 1s Converted to copper complex by heautmg naphthol-1:7-disulphonic acid and the resultant amino- It g 20 hours at tlelhperatfure h h j disazo compound is converted to the copper COI11P1X y wit an aqueous 50 0 ouplamrhonium S p a heating it with an aqueous solution of cuprammonium A solution of 19.3 parts of the trisodium salt of the sulphate for 20 hours at a temperature between 95 and coppfir'cohtammg ammodlsazo, p h so Obtained. m 0 C 15 250 parts of water is added with stirring to a suspension A Solution of 21 parts of the tetrasodium salt of the of 4.8 parts of cyanuric chloride in a mixture of 5 0 parts above copper complex in 230 parts of water is added with of acetone 100 Paris Q Water 11 200 parts of ice, the strring to a solution of 8.8 parts of the sodium salt of i g of the bemg ,mamtamed between 2-(3'-sulphoanilino)-4:6-dichlorotriazine in a mixture of and 5 by the addlhoh of 0 a 120 parts of water and 40 parts of acetone and the mixstirred for hour h a hetwheh 0 and 5 ture is then stirred at a temperature between 40 and F mlxthre 15 then nehtrahsed to H hy the for 21/2 hours the PH of the mixture being main addition of 9.2 parts of a 10% aqueous solution of sodium tained at 7 by the addition of a 10% aqueous solution of carhohhte' sodium carbonate. 80 parts of sodium chloride are then compound so ohtamed there 18 added, 3 of added and the dyestuft which is precipitated is filtered 25 Parts Of the sodlum 0f 3$u1Ph0flI111lne m Parts of off Washed with 10 parts of Water and dried on analysis Water and the mixture is stirred at a temperature between the dyestuffs so obtained is found to contain 0.9 atom of 1 45 Q 3 hours; PH of the mixture hemg organically bound chlorine for each disazo molecule presh h F 7 by the addmoh of a 10% aqueous 50h! ent. When applied to cellulose textile materials in conhon of bohhm carbohatejunction with a treatment with an acid-binding agent the 30 are then addhd h the dyestufi Whlch 1S Precipitated 1S dyestuff yields navy-blue shades possessing good fastness filtered off h dried to Washing and to light. On analysis the dyestulf so obtained is found to contain a 1.1 atoms of organically bound chlorine for each disazo Example 26 molecule present.

, terials in conjunction with a treatment with an acid-bindffl i zil f fiifig gs 32: a gg gf tg ing agent the dye-stuff yields navy-blue shades possessing supoan1ino-:1co 1 Gdft there are used 4.8 parts of 2-methoxy-4:6-dichlorotr1az1ne. i: gi g ig ig examples of the The y h so 9 h h apphed to cenhlose i shades obtained on cellulose textile materials from the niatqnals conlunctlon with a treatment d copper containing dyestuffs obtained by the procedure bmdmg agent Yields navyfblue Shades Possessmg goo described in Example 28 when the amino-disazo comfastness to washlhg and to hght' pound used in Example 28 is replaced by the amino-disazo Example 27 compound obtained by diazotising the primary amine listed in the second column of the table, coupling with In P151416 of the Parts Of the Sodlllm 5311 of the pa a-coupling amine listed in the third column of the Table, diazotising and coupling with the coupling component listed in the fourth column and by replacing the 3-sulphoaniline used in Example 28 by the amine listed in the fifth column of the table.

Shade on Example Primary Amine Para-coupling Amine Coupling Component Amine Cellulose Textile Material 29 g a eth s-sui ho- 2-methoxy-5methylaniline- 2-amino-8-naphtho1-3:6-di- 3'sulph0aniline Blue.

i i sulphonic acid.

,do 5-sul ph0-2-an1inobenz0ic Do.

aci 4-sulph0-2-amin0benzoic Do.

acid. 3-amino-5-sulpho-2hydroxy- D0.

benzoic acid. 4-sulplioaniline Do. Aniline-3:5-disulphonic acid. Do. Ammonium hydroxide Do. Methylamine. Do. fi-sulphoanthranilic acirl Do. 4-sulplioanthranilie acid-.." Do. 3-amin0-5-sulpho-2-hydroxy- D0.

benzoic acid. 2-methoxyanilinc 5-sulpho-2-aminobenzoic Do.

acl Aniline-2:5-disulphonic acid 2-methoxy-5-metliyl-aniline Ammonium hydroxide D0. 2:5-diehloro-4-sulph0aniline do 5-sulgho-2-aminobenzoic Do.

act 43 do do d0 3-amiuo-5-sulpho-2-hydroxy D benzoic acid. 3-chloro-4-methyI'6-sulph0- 2-methoxyaniline d0 fi-sulpho-il-aminobenxoic D0.

aniline. acidd do 3-sulph0ani1ine D0. d 4-sulph0aniline Do. 3-amin0 -5-sulpho-2-l1ydroxy- Do.

benzoic acid.

- shade on Example Primary Amine Para-coupling Amine Coupling Component Amine CIFHIIISSQ ext e Materials 48 z-naphtiiylamine-ezs-disul- 2-methoxy-5-methy1aniline.- 2-amino-8-naphthoi-3:6-di- -sulpho-2-aminobenzoic Blue.

phonic acid. sulphonic acid. acid.

49 2-naplithylaniine-5;7-disuldo o do Do.

phonic acid.

50 2-naphthylamine-4:8-disul- 2-amin0benzoic acid .d0 3-sulphoaniline Violet.

phonic acid.

51 Z-naplithylamine-fizB-disul- Zmethoxyaniline do -sulpho-Z-aminobenzoic Blue.

phonic acid. acid.

5.. .z-sulphoaniiine 2-methoxy-5-methylaniline. do 3:5-disulphoaniline Do.

53 2;5-disulphoani1ine .do 2-amino-5-naplitli 2-naphthylamine-4:S-disul- Navy-blue.

sulphonic acid. phonic acid.

54 2-naphthylamine-3;6;8 trido d0 3-sulph ne Blue.

sulphonic acid.

55 4-methyl-2-sulph0aniline do ssulpho-zaminobenzoic Do.

56 4-methoxy-2-sulphoaniline do 2-aniino-8-riaphtl'iol-3zddi- ---do Do.

sulphonic acid.

57 Z-aminobenzoic acid .do Q-aIninO-t'rnaphthOl-lfl-di- 3:5'disu1phoaniline Do.

sulphonic acid.

58 dsulgho-z-aminobenzoic .do do 3-sulphoaniline Do.

aci

59 2naphthylamine-5:7 disu1- 2:5-dimethoxyaniline "do d0 Do.

phonic acid.

60 2-sulplioaniline 2-methoxy5-methylaniline 2N-niethylamin0-5-napb 5-sulpho-2-aminobenzoic Navy-blue.

thol-1z7-disulphonic acid. aci

61 Aniline-zzs-disulphoiiic acid, do 2-arnino-5-naphtliol-l:7-di- 3:5-disulphoauiline Do.

sulphonic acid.

62 do do d0 5sul ph0-2-aminobenzoic Do.

ac 63 do do do 3-sulphoaniline Do, 64 do do do Mixture of ani1ine3z5-disul- Do,

phonic acid (3.3 parts) and 5sulpho-2-aminobenzoic acid (3.1 parts).

65 do .Jlo do W Q-naplithylamine-b;6:8-tri- Do.

sulphonic acid.

66 do do .-do 2-arninophenol-4z6-disul- Do.

phonic acid.

67 Aniline-2:4-disulphonicacid. lo -d0 3-sulphoaniline D0.

68 4chloroaniline-2-sulphon1c do 2 amino-8-naphthol-3tfi- .do Blue.

acid. disulphonic acid.

69 do do lo fi-sulphtrZ-aminObenzoic Do.

a 70 2-chl oroaniline-4-su1phonic do do 4-siilnh0aniline D 71 2-su1ph0arii1jne do 2N-methylamino-8-naph- 3-sulphoani1iiie Do.

thol-3 G-disulphonic acid.

72 4 chloro-5-methylani1ine-2r do.. do A ni Do.

phonic acid.

73 2-sulphoaniline Z-methoxyaniline do 4sulphoaniline Do.

Shade on Example Primary Aniine Primary Coupling Amine Coupling Component Amine (l glluiilise eir'ci e Material 74 4-methyl-2-sulphoaniline. 2-methoxy-5-methylaniline 2-amin0-8-naphthol-3z6- 4-aminobenzoic acid Blue.

(lisulphonic acid.

75 3chloro-4-methy1-6-sulphodo Do.

aniline.

76 d0 do ..do Equimolecular mixture of Do.

4-aminobenzoic acid and 5-sulphoanthranilic acid.

77 4-methyl-2-sulphoaniline do ..do Equimolecular mixture of Do.

4-aminobenzoic acid and metaiiilic acid.

78 do do do Equimolecular mixture 0! Do.

metanilic acid and sulphanilic acid.

I claim: lected from the group consisting of H and CH and Y is 1. The .disazo compounds represented by the formula: selected from the group consisting of amino, anilino, sul- X OH phonated naphthylami'no, sulphocarboxyan iline, sulphohydroxycar-boxyanilino, lower alkylamino, methoxy and C /\6 R N phenoxy, and the lzl-copper complexes of said disazo l compounds. H0as 7 i 2. The lzl-co-pper complex of the disazo compound g 65 of the formula: SOaII c I 01 (')CHa OH (I31 r 0 wherein A 15 a radical selected from the class consisting soaH of monocarboxy phenyl radicals, monosulphophenyl rad- 70 l lfiI I'd icals, disul-phophenyl radicals, disulphonaphthyl radicals, H035 SOHH trisulphonaphthy-l radicals, sulphocanboxyphenyl radicals and methylchlors ulphophenyl radicals Q is selected from (3H5 A N the group consisting of H, CH and CH O; X is selected I I from the group consisting of CH O and CO H; R is se- 75 $0311 SOsH 1 1 12 3. A mixture of the lzl-copper complexes of com- 4. The lzl-eopper complex of the compound reprepounds represented by the formula: sented by the formula:

I NH--C C-NH- SOaI-I l; l; N N 1 $0311 l N=N 011 1-10 I 01 SOaH NH N 10 1130- N=N 50m sour son; S0311 References Cited by the Examiner N=N 15 UNITED STATES PATENTS CH z 2,945,022 7/1960 Fasciati et a1. 260-153 2,993,038 7/1961 Fasciati et a1 260-153 SOaH 3,057,844 10/1962 Andrew et a1. 260153 XR 20 3,057,846 10/1962 Andrew et a1 260153 XR wherein X represents a radical selected from the group CHARLES PARKER Primary Examiner consisting of meta sulfoanilino and para sulfoanilino. R. J. FINNEGAN, D. M. PAPUGA, Assistant Examiners. 

1. THE DISAZO COMPOUNDS REPRESENTED BY THE FORMULA: 